Manufacture of fertilizer salts



June 24, 1930. H, B, K|PPER 1,768,075

MANUFACTURE OF FERTILIZER SALTS June 24, 1930.

H, B, KIPPER MANUFACTURE OF FERTILIZER SALTS Filed Jan. 14, 1928 2 Sheets-Sheet 2 TIE. E

TIE. E

Patented June 24, 1930 UNITED STATES PATENT OFFICE Application led January 14, 1928. Serial No. 246,807.

The present invention relates to the manufacture of ertilizing salts such as ammonium sulphate and ammonium phos hate, by interaction of gypsum or calcium p osphate on the one hand, with carbon dioxide and ammonia on the other hand, the reaction being carried out in the presence of water, and the reaction mixture being very intimately brought into contact with the reacting gases, while in a heated state.

It has heretofore been proposed to make ammonium sulphate by reacting upon a sludge of calcium sulphate, in the form of burnt gypsum, in the presence of water, with ammonia and carbon dioxide, but the processes heretofore proposed have not given entirely satisfactory results in ractice, since it has generally not been possi le to carry the reaction to a suilicient degree of completion,

thereby causing considerable loss of materials. y

In accordance with the present invention, l have found that the reaction can be carried to completion or substantially to completion,

by maintaining the liquid sludge at a suiiciently high temperature, and by giving a suiiicient contact of the sludge with the reacting gases, preferably by converting the sludge and maintaining the sludge in the condition 50 of almost a mist in the reaction chamber through which the gases travel.

In the annexed drawing forming part of this specification, Fig. 1 is a longitudinal section of the essential portions of the reaction apparatus.

Fig. 2 is a section showing the means for operating the stirring apparatus and the scraping apparatus, the section being taken a proxlmately on the plane 2--2 shown in i 3 is a section through the reaction cham er showing the agitators, beaters and sprayers and Scrapers.

Referrin now 1n detail to the apparatus shown in t e drawings, a stationary boilerlike reaction vessel 10 is provided constituting the main reaction chamber. ne end of the receptacle 10 is entirely closed by a plate 11 havlng a central opening` therein 12, 50 through which extends a steam pipe 13, having a plurality of radial branches 14, opposite ones of which are connected by perforated pipes 15, for introducing superheated steam rom the pipe 13 into and through the liquid sludge in .the reaction vessel 10. Carried upon the pipe 13 are a number of arms 17 to -sthe ends of which are attached agitating ythrough the reacting chamber 10, the ends 20 of the agitator blades 18 are curved as shown in Fig. 1. Gases containing ammonia and carbon dioxide are introduced through the pipe 21 adjacent one end of the reaction vessel 10, and the unused gases iind exit through the liue 22 at the opposite end of said vessel, which may lead to another reaction vessel for the purpose of recovering any ammonia still remaining in the gases.

The right hand end of the reaction vessel 10, as shown in Fig. 1 is largely open, but is provided with an annular partial closure 23 through which the excess of gases find exit, and over the lower edge of which the liquid or sludge iiows, the latter to nd exit through the pipe 2li into a settling or crystallizing tank 25. The material is drawn oil1 from this latter tank by the conveyer 26 to suitable purifying, concentrating or drying apparatus, depending upon the grade of purity required in the ammonium sulphate product.

Since agitation is necessary for converting the sludge into a mist, this agitationis fur-- nished by rapid rotation of the pipe 13 carrying the agitators 18 and the pipes 15 above described. For this purpose the end 27 of a superheated steam line 16 projects into one end of the pipe 13 through a stuffing box and any suitable means, such as the belt 28 and pulley 29, may be provided 'for imparting a high speed of rotation to the pipe 13 and the above mentioned members carried thereby. In practice I find that a speed of revolution of 600 revolutions per minute is very satisfactory for this y of a slud in this manner 1s likely to cause considera le deposition of solid material upl* on the wall of the vessel 10 and in order to prevent any excess of such accumulation, scrapers are also mounted Inside of the reaction vessel. The Scrapers 30 are con- `nected by suitable rings 32 and are caused to rotate in the reaction vessel 10 and rotate ata slow speed, say one or two revolutions per minute.

Rotation is imparted to the Scrapers 30 by an suitable means.

he means shown for this purpose is as `A pulley 33 is secured to the pipe 13 adja- 'cent one of its ends vand a belt 34 passes over said pulle shaft 36 o a reducing gear 37. The counter-` and a pulley 35 secured to the shaft 38 of the reducing gear 37 carries a s rocket wheel 39. A cham 40 passes over t e sprocket wheel 39 and a sprocket wheel 41 carried by a sleeve 42 which surrounds and is rotatable on the pipe 13 and extends into the reaction vessel 10. Arms 32a extending radially from the sleeve 42v are each connected to one end of one of the Scrapers 30, vand the opposite end of each of the Scrapers v `30 is connected to one of a series of similar arms 32? extending radially from .a sleeve 42a which extends through the end :wall l1 of the reaction vessel and surrounds and rotatable on the pipe 13.

y carried thereby as above indicated.

The pipe 13 is mountedin suitable bearings 44 for supporting this pipe andthe elements In carrying out the process,.either burnt or ground gypsum may be used as the initial solid material introduced at 21, vthis being simply crushed to a fine state of division, and sus ended in sucientv water to produce a slu ge which will flow readil when leaving v cined gypsum, ground to a powder. It is nolt necessary to previously calcine same,although such treatment is not precluded.

The gas entering by pipe21 may contain both carbon dioxide and ammonia if desired,

or in some cases the ammonia can be lirstremoved from the gases, say coke oven gases,

by washin in Water, and this water can be supplied elther through pipe 21 or pipe 19, or the lwater containing the ammonia may be vused for suspending the gypsum. By the intensive heating and agitating inthe receppurpose. The handling tacle 10, the sludge of psum and wateris` y intoegffine mist, very 'intimate contact gases flowing through the appara.-

converted almost who which is brought into with the tus.

Although for some reasons it may be desirable to heat the mixture of water and this is not always necessary- The operation; j l

when using y 'gy sum .ma bevcarried out at Say 20v to 35 valtii oug there is no objec tion to a higher temperature, say up .toy 60l v C., if desired. y v

As above stated, the sludge at the end of the reaction dam 23, and alls through the pipe 24 into the receptaclev 25, from vwhich it is removed through the casing of the helical conveyer 26, to a suitable ilterin apparatus, forv exfample a rotary Iilter, a ter which the solid,

consisting essentially of calcium carbonate,

eriod overflows the annular is washed to remove adhering ammonium sulphate, and the wash` waters, or some of them, can be used for making up the original Asludge of calcium sulphate to be introduced through the pipe 19. The ammonium sulphate can thereafter be concentrated and crystallized and vdried in anyl approved manner. l y

Instead of heating the reaction.4 chamber solely the steam, or as a substitute for this b mode o; heating, hot gases from any suitable source, for example coke ovens or the like, may enter the space 45, surrounding this reaction chamber, from flue 46 and leave through flue 47. v

' In a modified form of the process I can produce ammonium phosphate, say` monoand di-ammonium phosphate (the formerv being, if desired, later treated with ammonia to form diammonium phosphate), by

' substituting calcium phosphate, in the form-v of finely pulverized lphosphate rock, in agueous suspension, instead of the sus nsion o gypsum. In such a process I wou d preferably use one part of calcium phosphate to about 3i to 5 parts of Water, in mixing up the original sludge to be employed. In this modification, a temperature of 30 to 60 C. gives very satisfactory results. I Likewise, instead of using the phosphate rock alone, I can mix this with a quantity of calcium sulphate, say gypsum, and treat the mixture of calcium phosphate and sulphate by the process, to produce a mixture of ammonium phosphate and vammonium sulphate, for use in the vfertilizer industry.` A The apparatus described and shown here- 485 and 739,040, of which the cation is in part a continuation..

The entire apparatus may be made of iron or steel, although alloys which are more resistant can be usedif desired. Thus the receptacle 10 and the parts therein can be made of they nickel alloy Hybnickel alloy.

I have above referred to the introduction of steam through the hollow shaft 13, but it will be understood that other hot gases can be similarly introduced if desired, and these gases may, if desired, contain the carbon dioxide for eecting the reaction or a portion of the same.

The gases introduced through pipe 21 may convenlently be coke oven gas, coal gas or the like, and if these gases do not contain a sulicient amount of carbon dioxide, this latter can be added thereto, either as carbon dioxide or as chimney gases, lime kiln gases or the like, if available.

I have above referred to withdrawing the entire material from tank 25 through the conveyer 26. If desired, however, a large quantity of material may be maintained in the tank 25 in order to allow the calcium carbonate to settle out therein, and this settled out calcium carbonate may be withdrawn through the conveyer 26, while the more or less clear liquor is Withdrawn through pipe 50, to a filter or evaporating pan, vacuum pan and the like.

I claim In the process of manufacturing ammonium salts from gypsum and phosphate rock by reaction therewith with ammonia, carbon dioxide and water, the stepwhich comprises beating such reaction mixture to a ne mist in the presence of steam in order to facilitate the chemical reaction between the constituents, and then separating the soluble from the insoluble salts.

In testimony whereof I have hereunto set my hand.

HERMAN B. KIPPER. 

